Hair and fur dye



' Patented July 14, 1925.

WOLF KBI TGHIVSKY AND WILLIAM K. NELSON, F (JHIGAGO, ILLINOIS.

mun AND run DYE.

10 Drawing.

To all whom it may concern:

Be it known that we, Wow KRITOBZEVSKY and WILLIAII K. Nnnson, both citizens of the United States, residin at Chicago, in

the county of Cook and Hair and Fur Dye, of which the following is a specification.

Our invention relates to the artificial colgring of hair, and particularly to a novel Hair dyes have been used since earl in the history of civilization. In earlier times the substances generally employed for this purpose consisted of the salts of metals, such as lead, copper, silver and iron;. also vegetable extracts, such as that of henna, reng and nuts of various kinds containing galhe and pyro'gallic acids.

dyes were composed of para or ortho di amines, amino phenols or naphthols and trihydroxy derivatives of benzene, as well as o diamido phenols. The satisfactory results'obtained by the use of these organic dyes are explained by the fact that each has the inherent property of oxidizing when exposed to. the air or to the action of oxidizmg agents. In the process of oxidation of these compounds, new chemical compounds result which are highly colored and insoluble in water, and when deposited on the hair they impart thereto the desired color.

H air dyes prepared from the specified compounds leave little to bedesired from the tinctorial point of view, but they are highly poisonous and are likely to cause serious harm to the users. This is now; well known and the eifects are described in the workb Erdman and Tomashevsky (Munch.

Med. och. 1906).

Much experimentation has been carried on with the idea of eliminating the toxicity from the described compounds. In that connection, a rule is given in the book by Dr. S. Ifi'ankel, entitled Arzneimittel Syn these. He states that cyclic hydrocarbons,

tate of Illinois, have invented a certain new and Improved In modern times, the more popular hair Application Med December 80, 1924. Serial No. 758,852.

amines or phenols, which are known to be poisonous, lose partially or completel their toxicity after replacing one of their hydro- 60 gen atoms with a group of an acid character. As an instance aniline is cited, which is poisonous, while sulphanilic acid and anthranilic acid are perfectl harmless. This princi 1e was applied by r. Erdman as a basis or a series of hair dyes consisting of the sodium salts of aminophenolsulphonic acid, of aminodiphenylaminesulphonic acid etc. These dyes have had very limited success, for the particular reason that the shades obtained by their use are not natural; further, the acid group introduced into the compounds weakens their tinctorial strength. Still another objection is that the final products of oxidation are generally of a soluble nature and are easily washed out.

Our discovery is that by obtaining, at a 4 certain stage, the metallic salts, the tinctorial value is greatly increased,.and dark shades having a natural appearance are obtained, and are fast relative to light and water. The results obtained by us are in accord with the theory of mordants and of the formation of lakes from dyes combined with certain mineral salts.

When a sulphonic or carboxylic acid of an aminophenol or of an aminonaphthol and their derivatives, as amino and arylamino,

of a diamine and its derivatives, as amino and arylamino or of a polyphenol, or their 0 respective sodium salts, is combined in S01? tion with a salt of a metal such as. iron, copper or chromium, or any other substance having mordanting properties, no

change in the molecular structure of the organic radical takes place unless there is an oxidizin agent present. Whether 1t1s by means 0 the oxygen from the air or by the use of various oxidizing materials, as soon -.as oxidation sets in, the change of the organic radical into a chmone structure begins. This chan (1 form when combined with the metallic salt results in a highly colored insoluble compound.

ence of an oxidizing agent the change in the structure of the organic radical and the -formation of the iron salt of the chinone sulphonic acid proceeds very rapidly, thus:

OH O

r l I 3 mi, 11 1111 om dome 0.11 w

Itwillbeseenthattheironinthisre- .action becomes oxidized to the trivalent variety. This highly colored insoluble compound fixes itsel to the hair, impartin to it a dark shade-of natural a pearance.

. e .fact that the dye is mor anted makes it fast to light and water. A

i We have observed, in our work, that in the case of the metallic salts which possess a lower and a higher state of oxidation,

such as in the case of iron and copper, the

oxidation of the organic radical proceeds at a much faster rate and more completely thanin thecase of where metals aving only one state of oxidation are used. The reason for this can be ascribed to the fact that metallic salts having a capability of forming higher stages of oxidation are usually much more oxidizable than the organic radicals. They thus act as oxygen carriers by first assuming a higher state of oxidation and then acting on the organic radical as an oxidizing agent. Meanwhile, they are being reduced in this manner to the lower state, and the process is repeated un til complete oxidation of the organic radical and the metallic combination of the chinone acid takes place.

In reparing the solution of our dye,care must exercised to have the. proper hydrogen ion concentration. If the solution is too alkaline, premature. oxidation takes place, as well as precipitation of the metallic salt. If on the otherhand, the solution is too much acid, there is'a tendency for the organic acid have found that a very slight alkaline reaction on turmeric test paper'is the right point bf hydrogen ion concentration in our solution.

As alkali reagents in which to dissolve our organic acid, we may use carbonates,

h droxides, ammonia, borates, borax, phosp ates, soluble salts of amino acids, acetates or sulphites.

As acidifying reagents, we may use organic acids and acid salts such as citric acid, formic acid, acid tartrate, acid sulphite like sodium bisulphite, acid sulphate like nitre cake. l

radical to precipitate out. We

' We claim:

The following examples illustrate the preparation of the product:

. 30 gms. 1:2 naphthalenediamino--sul phonic 'acid- 10 gms. potassium h droxide.

iwgms. potasm'um bic romate. ater to make one litre.

10 gms. ferrous sulphate. 20 gms. borax.

5 gms. sodium hydrogen sulphate. Water to make one htre. I

40 gms., monobenzylparaamidophenolsulphonic-aci I a 60 gms. sodium sulphite.

10 gms. manganous sulphate.

15 gms, sodium hydrogen sul hite.

Water suflicient to make one 'tre.

The above in reasonable imits and we anticipate makqluantities may be varied with- 4 ing various combinations of this class of compounds for the purpose of obtaining various shades.

The method of application of our preparation is by brushing the same on the hair with a small brush and subsequent exposure to the action of the' oxy en in the air; or, ance; or by mixto an electric drying app ing the hair dye immediately before use with hydrogen-peroxide or other rea ents capable of giving ofl' hydrogen peroxi e or oxygen; or by treating the hair after or before the dye wasb'rushed on with hydrogen peroxide or other oxidizing agents.

1. A hair dye. in the form of a colorless aqueous solution, consisting of the reaction products of an organic cyclic compoun belonging to the aromatic series of the general iormula in which 0 standsfor an aromatic cyclic hydrocarbon and its homologues, in which R stands for an hydroxyl group, or an amino group and its substitution products, the position of the radicals being such as to be capable of forming a quinoidal structure, in which AC stands for an acid grouping, the position of the acidic group to the other radicals bein immaterial; together with a metallic sa t capable of acting as a mordant, an alkaline reacting substance to dissolve the organic to each other acid and form a salt, and an acid reacting substance to neutralize the excess alkalinity, so that the solution is substantially neutral.

2. A hair dye consisting of a Water solution of 1:2 naphthalenediamine--sulphonic acid, ferrous sulphate, borax and sodium acid sulphate;

Signed at Chicago, December, 1924.

I WOLF KRITCHEVSKY.. WILLIAM NELSON;

111., this 15th day of 20 

